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Solvothermal processes are defined, and the different domains of applications are described. The
main physico-chemical factors playing a key role in such processes are then analyzed. The trends
characterizing the current development of solvothermal processes are outlined.
morphology of CdS nanoparticles was studied using The structure and consequently the morphology of the
Cd(NO3 )2 · 2H2 O and (NH2 )2 CS (or Na2 S) as sulfur resulting CdS crystallites is induced by the release of
sources. Without ethylenediamine, a spherical mor- S2− into the reaction medium. With Na2 S ·9H2 O, due
phology was detected, but with the addition of (en) to its solubility leading to a high S2− concentration, the
more accelerated growth along the 001 direction was kinetic factor induces the formation of the metastable
observed [29]. The formation of such nanorods was ex- zinc blende structure. On the contrary, with thiourea
plained by the complexation in [Cd(en)3]2+ . The exis- and sulfur, the slow release of S2− favors the thermo-
tence of an intermediate compound (CdS ·0.5en) with a dynamically stable wurtzite form.
3D network could initiate, as a template, the elongated
morphology of CdS nanocrystallites [30]. Solvothermal topotactic reactions induced
Solvent effects are also important in solvothermal by quasi-insoluble reactants
processes involving organic chemicals. Biodegradable
In the majority of cases, solvothermal processes in-
polymers have recently gained more attention as a po-
volve the dissolution of the reactants. Consequently, all
tential substitute for conventional synthetic petroleum-
structural correlations between reactants and products
based polymers [31]. Poly(L-lactide) (PLAs) was ob-
are lost, and only chemical species in the solution can
tained from the ring-opening polymerization of L-
play a role.
lactide through a solvothermal process using SnCl2 as
If one of the reactants remains in the solid state
the catalyst for the polymerization reaction. The nature
under solvothermal conditions (in particular for low-
of the solvent is one of the important factors because
temperature syntheses) it becomes possible to initiate
it can promote the solubility and reactivity of com-
the structure of the final product through the insol-
pounds and complexes at elevated temperatures under
uble reactant. Such a solvothermal route was called
high pressure [10].
“structure-inheriting solid-state reaction” by Whit-
These examples have demonstrated that the selec-
tingham [33]. The synthesis of CoMoO4 through a
tion of the chemical nature of the solvent appears to
solvothermal process (using water as the solvent) was
be an important factor, allowing to control the result-
investigated as a function of the reaction time using
ing structural form in materials chemistry or to direct
MoO3 and CoO as precursors at 453 K. MoO3 is com-
the morphology of the nanocrystallites in materials sci-
pletely dissolved within the first step (∼ 5 min) of
ence.
the hydrothermal treatment leading to the formation
The Role of the Chemical Nature of the Reactants of CoMoO4 · 3/4H2 O. Upon increasing reaction time,
in Solvothermal Processes the high-pressure form of CoMoO4 (hp-CoMoO4) ap-
pears, accompanied by a gradual disappearance of
Impact of the solubility of the reactants CoMoO4 ·3/4H2 O. hp-CoMoO4 is the most dense form
of the three structural forms (α , β , hp-CoMoO4).
In materials chemistry, for the same solvent, the re-
Consequently CoMoO4 · 3/4H2 O initiates the hp form
action can be governed by the concentration of chem-
through a pseudo-topotactic reaction during the hy-
ical species in the reaction medium, this concentration
drothermal process.
being directly correlated to the solubility of the reac-
tants.
Stabilization of intermediate species as templates
In the solvothermal synthesis of CdS using ethylene- through solvent/reactants interactions
diamine as the solvent, the same cadmium precur-
sor (Cd(NO3 )2 · 4H2 O) but different sulfur sources The chemical interactions between reactants and
[Na2 S ·9H2 O, thiourea, sulfur] can be selected as an solvent can induce the formation of intermediate
illustration [32]. The nature of the sulfur source plays species which are able to influence the morphology of
an important role either on the CdS crystal structure or the resulting crystallites.
the morphology of the resulting crystallites. Such re- For example, during the solvothermal synthesis of
sults can be explained by the reaction process in two metal selenide crystallites, using metal chlorides (or ni-
steps: trates) and selenium powder as reactants and hydrazine
hydrate as the solvent, the formation of an intermedi-
(1) Cd2+ + 3en → [Cd(en)3 ]2+ ate species has been suggested to explain the observed
(2) [Cd(en)3 ]2+ + S2− → CdS + 3en. 1D morphology of the resulting crystallites [34]. The
1002 G. Demazeau · Solvothermal Processes
NH2 -NH2 group may act as a bridging bidentate lig- ethanolamine and water as solvents [44]. L-Cysteine
and between two different cationic clusters and lead to acts both as the sulfur source and the coordinating
intermediate species able to initiate a 1D morphology. agent due to the presence of NH2 and HS groups.
Formation of intermediate compounds which are able The Role of the pH Value in Different Solvothermal
to modify the kinetics of the reaction Processes
In some cases, the intermediate chemical species For processes in solution, in particular solvother-
stabilized during the solvothermal reaction are able to mal processes, the pH value can play different roles
modify, according to their stability, the kinetics. Con- [45 – 47].
sequently, the phase evolution to the final crystallites For example, it can
can modify the nucleation and the crystal growth steps
and therefore their size and morphology. – help in the preparation of specific compositions in
The preparation of yttrium aluminum garnets (YAG) materials synthesis,
using a solvothermal process with ethylenediamine as – induce the stabilization of specific structural forms,
the solvent and yttrium and aluminum nitrates as reac-
tants can be used as an illustration [35]. – control the size and the morphology of the crystal-
lites, or
Two different precipitants have been used to pro-
duce hydroxides as precursors: urea and ammonium – facilitate the elaboration of nanocomposites.
hydrogen carbonate. With urea, the formation of YAG
implies a transitory step with the intermediates YAlO3 In particular the influence of the pH value on the
and Y4 Al2 O9 , but with ammonium hydrogencarbon- coordination geometry of the transition metal and the
ate, hydroxides are directly converted to the pure YAG coordinating mode of the ligands has been investigated
phase. In this last case, a better dispersity and smaller for the synthesis of hybrid materials between transition
crystallites are observed. metals and polymers.
observed in the temperature domain 500 – 550 ◦C. With ation is a fast internal heating able to induce a fast nu-
the same reactants, but replacing benzene by mesityl- cleation.
ene as solvent, a higher crystallization temperature is Some correlations have recently been delineated be-
required. This temperature increase leads to a large tween the microwave power and the morphology of
amount of carbon incorporated in the nitride structure ZnSe crystallites (a material for optoelectronic de-
due to solvent decomposition [49]. vices) [62]. Using the same experimental conditions
In molecular chemistry, paramagnetic clusters are (nature of the reactants, nature of the solvent, temper-
prepared through conventional processes using the ature and pressure conditions), the anisotropy of the
mixing of metal ions and ligands in a common solvent ZnSe crystallites increases with the microwave power.
at a temperature limited by the boiling point of this sol- To prepare hybrid materials, the comparison of con-
vent at atmospheric pressure. New preparative routes ventional heating and microwave heating has shown
based on solvothermal methods have been developed that the crystalline quality and the yield of the prod-
at higher temperatures [50 – 52]. uct are obviously better with a shortened reaction
Recently the effect of the cooling rate was time [63].
demonstrated in the solvothermal synthesis of ZnO Combined sonochemical-solvothermal processes
nanorods [53]. have also been developed in particular to pre-
pare nanocrystallites and metal organic frameworks
The role of pressure
(MOF9 ) [64, 65].
In solvothermal processes, pressure can play differ-
ent roles: (i) the stabilization of more dense structures, Associated Methods to Prepare the Reaction
if the pressure range is large enough, (ii) the enlarge- Medium
ment of the thermal stability domain of the reactants,
Different methods for the preparation of the reaction
and (iii) the enhancement of the chemical reactivity medium have been investigated during the last years, in
and of the kinetics of the involved reactions. particular in materials chemistry (synthesis of new ma-
The solvothermal synthesis of Sb2 S3 from SbCl3 terials) and materials science (to obtain nanoparticles
with thiourea as the sulfur source and methanol as the with controlled size and morphology), for example
solvent can be used as an illustration of a pressure-
controlled formation of nanorods [54]. – solvothermal pressure-relief where the gas pro-
The solvothermal preparation of CuO and Cu2 O duced in the high-pressure vessel is controlled [66],
nanocrystallites using Cu(II) acetate, Cu(CH3 COO)2 , – solvothermal scission-template-transportation with
as the precursor and water as the solvent was in- the formation of an intermediate compound acting
vestigated depending on the imposed pressure value. as the template [67],
The pressure increase seems both to hinder the ef-
– extraction solvothermal methods [68],
fectiveness of the reduction phenomenon induced by
CH3 COOH (with the partial formation of CuO) and to – phase-transfer catalysis [69],
affect the morphology of the crystallites [55]. – sol-solvothermal processes where the mixture of
Associated Technologies precursors is prepared as a sol [70],
introduced into the autoclave at 300 ◦C and 10 MPa, Development of hydro/solvothermal crystal growth
the content and crystallinity of c-BN can be improved processes
by increasing the RN value [72].
The preparation of single crystals for functional ma-
Recent Trends in Solvothermal Processes terials is always an important domain for various in-
According to recently published papers, different re- dustrial applications. In particular GaN and ZnO have
search domains have been strongly involved in the de- received increasing interest from both fundamental and
velopment of solvothermal processes. technological points of view [95 – 98].
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